Polymers and copolymers of nu-pyridyl amide of an alkene-1, 2-dioic acid



Patented Aug. 24, 1954 POLYMERS AND COPOLYMERS 0F- N-PYRI- DYL AlVHDE ACID .OF AN ALKE-NErLZ-DIOIC Gaetano F. DAleli'o, Pittsburgh, Pa., assignor to Koppers Company, .Inc., a corporation of Delaware No Drawing. ApplicationAugust .31', .1951,

Serial No. 244,699

15 Claims.

This invention relates to :newsmonomersand. to new polymeric materials derived therefromiand: is particularly directed tdther'aolymerization products'obtained by polymerizing a mass comprising asanew monomer an N-pyridyl. amide of: an ethylene alpha, beta-dicarboxylic acid. hereinafter referred. to as. apolymerizable ethenedioic acid and a copolymerizable compound especially acrylonitrile. The invention also relates to compositions of these polymerization products adapted to the formation of shapedi'articles; in many cases to molecularly oriented shaped articles, particularly to fibers,xthreads;. bristles, mono-filaments, etc., hereinafter referred to as fibers, and other shaped article such as films and the like, which articles show' improvedi dyeing properties.

It has been known for some time that certaincopolymers of acrylonit'rile'may be adapted to thepreparation of shaped articles,1.such.as' films;

fibers, foils, tubes, etc. Some of these-copolymers have been regarded. as capable: of being colddrawn to produce structures molecularl'y oriented:

along the fiber axis. Cold-drawing may-be defined as the stretchingof a polymeric material-at a temperature below themeltingpoint ofthemazterial to give a molecularly oriented structure.

The resistance of acrylontrile polymers. todyes of" all types has. presented serious dyeingproblems, especially in the development of synthetic fibers from these polymers. In fact, in order to dye polyacrylonitrile one commercial process resorts to the use of high pressures with water solutions or organic d'mpersicns of dyes; It has'been proposed that improvement in dye'susceptibility can be obtained by the use of itaconic acid in small amounts as copolymerizingmonomer in the preparation of acrylonitrile polymers. How-- ever, the polymer products obtained thereby have a' tendency to crosslink upon standing at temperatures of at least about 70-80" C. or-upon spinning from hot solutions. spo'liation of material by gelation during'st'orage, embrit-tlement offibers, fouling of 'spi-nningjets; and other production difficulties.

In accordance with the present invention it has now'been found thatcrosslinking may" beayoicled and that improvements in dyeing properties of acrylonitrile polymers are obtained by' the polymeri'zation of monomeric masses comprising acrylonitrile and an-N-pyridyl-amide of apolymerizable ethenedioic acid with orwithout other copolymerizable ethylenic compounds. It' has been found further that in addition't'o'the fact that the N pyr'idyl amidesof--polymerizable Suchcrosslink-ing. causes acidi chloridewitli Zf amino-pyriGine. I i chloride'andanhydrideare sufficiently'reactive to ethened-ioic acids yield particularly valuable copolymers with acrylonitrile, they may also be used effectively to form" copolymers with other types of copolymerizable ethylenic' compounds} having a- CHz *C group. Thus it has been found. that valuable polymerization pro ducts may be'pre'-' pared in accordance with the invention by polyf merizing a monomeric mass comprising arr-N pyridyl amide of apolymerizable ethenedioicacid and a polymeri'zable compound such as acrylonitrile and the other polymerizable ethylenic'compounds-listed hereinafter.

The amides-of this invention may be formed by reactingan amide-forming pyridine, that is; an amino-pyridine having replaceable N-hydrogen with a polymerizable ethenedioic acid, or the anhyd-ri'd'es or'acid chlorides of these acids. The

readily polymerizable ethenedioic acids includemaleic' acid; fumaric acid, citra'conic acid, and mesa'conic acid. 'Iheseacids may be represented by the general formula H'OO C'CH=CRL"C O OHE which R'" is either hydrogen or the m'ethyf radical. (The formulas herein are not intended to distinguish between cis and trans forms.) Since the 'ethenedioic acids aredibasic; oneof the; carboxyl groups can be esterifi'ed either before-or after amidation. Another amide'groupsimilarly maybe introduced either before or after theamidation. The amid'ati'on may als'obecarried t'dthe diamide stage. When it is carried to the mono-- stage only, the remaining carboiiyl'group may'be' esteri'fi'ed or amid'ated (with ammonia or'another amine) as desired.

For-reasons ofeconomy and ease of preparation the methylior'ethyl ester of the N -(2-pyr'id'yl'l amide acid is usually preferred when an ester" i's used and hasthe formula in which R ise'ither'the methyl or ethyl radical. These: esters are prepared simply by refluxing methanol or ethanol. with the proper anhydride t'o'form' the acid ester and the acid ester formed is'then' converted to. the acidchloride' by refluxing. with thionyl chloiide and the acid chloride.

formed" is thereafter reacted with 2-aminopyridine to produce the desired'ester, that is, theimethyl'or ethyliester of. theN-(Z-pyridyl) amide acid. The amide-acid itself is convenientlyzpre pared by reacting the proper anhydride or the" The acid form the above esters or amides merely upon the mixing at room temperature. In some cases where the acid chloride or anhydride is not as reactive or in order to get more complete reaction, gentle heating may be advantageous. As an alternate synthesis of the ester-amid, the amideacid can be readily converted to a sodium or potassium salt and esterified with dimethyl or diethyl sulfate to the corresponding ester.

The N-pyridyl amides of polymerizable ethenedioic acids may be represented by the formula CR'CO Y (JHCO]Z in which Y is the radical Z or the radicals R- or R2N in which R is hydrogen or the alkyl, aryl, aralkyl, alkaryl or cycloaliphatic groups which may have halogen, acyloxy or alkoxy substituents or when Y is R2N the Rs may be linked together to form with the nitrogen a heterocyclic group; R is hydrogen or the methyl radical; and

Z is the group NR"P in which R, is hydrogen or an alkyl group, such as, methyl, ethyl, iso propyl, n-butyl, sec-butyl, amyl, hexyl, decyl, and the like, advantageously containing less than 4 carbon atoms and P is a pyridine nucleus. The pyridine nucleus may be substituted or unsubstituted. If substituted, it is preferred that the substituents be hydrocarbon group or groups containing not more than a total of 5 carbon atoms as in the case of the monoethyl pyridines, the dimethyl pyridines, the diethyl pyridines, the methyl ethyl pyridines, isoquinoline, quinoline, and the alkylated quinolines such as quinaldine.

When the amides used in the practice of the invention contain an ester group or an amide group other than group Z, the radial R may be methyl, ethyl, propyl, isopropyl, n-butyl, sec.- butyl, amyl, hexyl, decyl, chloromethyl, chloroethyl, cyclohexyl, methyl-cyclopentyl, propylcyclopenyl, amyl-cyclopentyl, methyl-cyclohexyl, dimethyl-cyclohexyl, chloro-cyclohexyl, phenyl, chlorophenyl, Xenyl, naphthyl, tolyl, chlorotolyl, xylyl, ethyl-phenyl, propyl-phenyl, isopropylphenyl, benzyl, chloro-benzyl, phenethyl, phenylpropyl, phenyl-butyl, acetoXy-ethyl, chlorophenoxy-ethyl, acetoXy-propyl, acetoXy-isopropyl, acetoxy-phenyl, acetoxy-benzyl, acetoxy-cyclohexyl, methoxy-propyl, methoxyphenyl, methoxy-benzyl, methoxy-tolyl, methoxy-cyclohexyl, etc. or part of a heterocyclic amino group, such as, the piperidyl, piperazino and morpholino groups.

The proportions of the amide in the polymerization products of the invention may vary over a wide range, ranging from equimolar proportions of amide down to very small amounts of amide such as may be employed in acrylonitrile polymers to impart dye susceptibility thereto. Although even smaller amounts are somewhat efiective, the improvement in susceptibility of acrylonitrile copolymers to dyes becomes particularly noticeable when the amide content of the copolymer is about 0.1 per cent and the susceptibility increases as the amount of amide is increased. Ordinarily sufficient improvement in dye susceptibility is obtained with amounts of amide ranging up to about or per cent but it may be advantageous for reasons such as in the preparation of ion-exchange polymers or additives to improve dyeing properties to have a higher proportion of amide in. the acrylonitrile copolymer. m such cases the concentration of amide may range up to or approaching mole per cent. Within these proportions acrylonitrile acetoxy-tolyl,

copolymers of the invention show great afiinity toward many dyes especially basic, acidic, vat, and cellulose acetate dyes.

In addition to the improvements effected in the resulting copolymers, the use of the N-(pyridyl) amides has certain other advantages over the use of the corresponding acids. For example, the amides are more soluble in acrylonitrile than the acids. Therefore, it is generally easier to get complete copolymerization of the amide with acrylonitrile in solution, emulsion and suspension polymerizations. Still further advantages accrue from the presence of these amides. Thus when non-esterified monoamides are used the copolymers of the invention show high susceptibility to basic dyes.

The acrylonitrile copolymers discussed herein are soluble in N,N-dimethyl acetamide (DMA), N,N-dimethyl formamide (DlVlIE) butyrolactone, ethylene carbonate, N,N-dimethyl methyl urethane of the formula (CH3)2NCOOCH3, ethylene carbamate, N-methyl-Z-pyrrolidone, and a num ber of similar solvents, used alone or in conjunction with N,N-dimethyl cyanamide, N,N-dimethy1 cyano-acetamide, N,N-dimethyl methoxy-acetamide, methylene dinitrile, methylene di-thiocyanate, formyl caprolactam, formyl morpholine, tetramethylene sulfone, etc. Nitroalkanes, such as nitromethane, may be used as solvents for such copolymers having no more than about per cent acrylonitrile, providing the comonomers used in preparing such copolymers do not have substituent groups of equal or greater secondary bonding force than the eyano groups in acrylonitrile. Copolymers of the present invention which have high proportions of monomers of relatively low secondary-valence bonding strength, such as vinyl chloride, may often be dissolved in acetone or mixtures of acetone and solvents of the above types.

This invention will be more fully described by the following examples which illustrate methods of practicing the invention. In these examples and throughout the specification, parts and percentages are intended to mean parts by weight and percentages by weight.

Example I Five polymers of acrylonitrile are prepared from the following monomer compositions:

N-(2-pyridvl) malelc on his acid, parts Acrylonitrile, parts The 100 parts of monomer or monomer mixture is, in each, slowly added over aperiod of less than an hour to 750-1000 parts of distilled water at 30-50 C. containing dissolved therein one part of ammonium persulfate, 0.6 to 1.5 parts of sodium bisuliite and 0.5 part of sodium dodecylbenzene sulfonate. The reaction is continued for 2-6 hours, at which time a yield of about per cent solid polymer is precipitated. The resulting polymers have molecular weights over 10,000. Each polymer is dissolved in N,N-dimethyl acetamide or butyrolactone and a film cast from each solution.

A water solution of methylene blue dye (a basic dye) is prepared by making a paste of the dye with l per cent by weight dye solution. This 51 dye solution is keptboilin'g for one hour While the aforementioned films are immersed therein forone hour. The dyed films are then removed and separately subjected to washing withboiling Water for one hour, the boiling water being changed frequently to remove the desorbed dye. The unmodified polyacrylonitrile film shows only alight tint, whereas the mono-N-(Z-pyridyl) maleic amide acid copolymers are a deeper and denser shade. Identical films, cold-drawn and heat-treated, show dyeing characteristics similar to the undrawn films.

Fibers are spun from the same N,N-dimethyl acetamide or butyrolactone solutions either by dryv spinning or by wet spinning, into. glycerine baths. solvent and dried. After cold-drawing: the, dried fibers 600-900 per cent at 120-l4.5 C..and.subsequentlyv heat-treating them. at. 150 C. for one hour, the fibers are given the same dyeing and.

washing treatmentdescribed above with the same results as for the films, a light tint being aoquiredv by the unmodified polyacrylonitrile, fibers and a deeper and denser color being given to the maleic copolymer fibers of this invention.

Instead of N-(2-pyridyl) maleic amide acid,

the various N-(Z-pyridyl) amide acids disclosed abovemay be used.

Example II Five polymers of aorylonitrile are prepared from the following monomer compositionsz.

To 900 parts of water, adjusted to. a pH, of about three,,in a suitable reactor, is. added 10 part of ammonium. persulfate, 0.5 part of sodium bisulfite, and 100 parts of monomer, or monomer mixture. The reactor is then flushed with deoxygenated nitrogen and heated with.

agitation to 50 C. for 24 hours. Steam is introduced into the reactor to remove unpolymerized monomers from the mixture. A small amount of aluminum sulfate is added to, the mixture and the polymer isolatedby filtration.

The polymer is then washed with water and with methyl alcohol. A portion, of the. polymer is dissolved in dimethyl, iormamide or butyrolactone and a film castfrom the solution. film. is washed entirely free of solvent and stretched. at a ratio of about. 8:1 inv a glycerine bath at 135 to 145 C. The film is then washed in water. and. dyed in a bathoontaining for. each part of film 0.05 part of 1,5-diamino-4,8'-dihydroxyanthraquinonc-3-sulfonic acid, 0.03 part sulfuric acid and 50 parts water (50:1 bath-film ratio) at boiling temperature for one hour. The film is then removed and washed with water and scoured for 15 minutes in a 0.4 per cent soap solution at 85 0. Whereas the, unmodified polyacrylonitrile. when treated in this manner has little or no color, all of thecopolymers are. dyed.

to a deeper blue shade.

Fibers are spun fromthe same solutions either by. dry spinning, or by wet spinning. The fibers are substantially freed from solvent and dried.

After cold-drawingthe dried fibers600-900per The fibersv are substantially freed from.

' scribed; aboveww-ith the same results for the films, a light tint being acquired by the unmodifieol polyacrylonitrile fibers and a deep and dense color being given to the copolymer fibers. The polymers of' this example are also soluble in dimethyl formamide, dimethyl acetamide, tetramethyl urea, butyrolactone, ethylene carbonate, formyl morpholine, etc.

Instead of the monomethyl maleic ester amide of the above example, various other esters of the maleic amidelacid may be used, such as the ethyl, propyl; isopropyl; butyl isobutyl, tertiary-butyl, hexyl, tolyl, phenyl, naphthyl, cyclopentyl, cyclohexyl, benzyLphenethyl, etc. esters. Likewise the esters of the other N-pyridyl maleic amide acids disclosed above maybe used.

Example III Five. partsrof'the copolymer fiber C of Example II. is dyed to: a deep; green shade using the vat color,'dimethoxy-dibenzanthrone at '70 C. in a bath containingobpartof dye, 0.25 part sodium hydroxide, 05; part sodium hydrosulfite and 100 parts-of; water (20:1 bath-fiber ratio). the first minutes of heating, 0.25 part of Glaubers salt is: added. The sample is then oxidized: in. a 0.5 per cent sodium dichromate 1.0 per centacetic acidaqueous solution at 70 C. for ,30 minutes in a :1 bath-fiber ratio. The dyedfiber' is thenscouredin a 0.5 per cent boil.- ing soap solution. A sample of yarn prepared from-theunmodified acrylonitrile polymers and dyed under the same conditions acquired only alight". shade ofcolor.

If 1,5 di p-- anisoylamino 4,8 dihydroxyanthraquinone is.-used.as thevat dye, the copolymer fiber-is'dyed a strong Violet color.

Example IV The procedure ofExample I is repeated for the. polymerization of the following monomer compositions:

\ Methyl ester of Acrylo- Vinyl N 2 1 C 1 r Polymer nitrile, Chloride, 'P Y) 0P0 i Parts Parts nziizleliclagf'ijle Soluble 111 A :92 5 3 DMEDMA,

. etc. 87 10 3 DlViF, DMA,

e c. 82 15 3 DB/ll, DMA,

- e c. 77 '20 3 NOzMe. 57 3 NOzMe. 37 60 3 Acetone.

Sometimes copolymers D and E, when dissolved in nitromethane may have gelled, partially dissolved particles knownas fisheyes. In such cases, the solubility may be improved by the addition of small amounts of materials which are good solventsfor acrylonitrile polymers, such as butyrolactone, ethylene carbonate, dimethyl form- After The procedure of Example I is repeated for the polymerization of the following monomer compositions:

A St lllldethgl ester 1?! yreue, -DY Y Polymer ,3 Parts maleic amide r 5 acid, Parts Dyeing tests of these copolymers show improvements in dye susceptibility similar to Example I. In place of styrene, various styrene derivatives may be used, such as alpha-methylstyrene; nuclear-substituted chloro-styrenes, i. e., ortho-, meta-, and para-chloro-styrenes, dichloro-styrenes, for example, the 2.3-, 2,4-, 2,5-, 2,6-, 3.4-, and 3,5-dichloro-styrenes, trichlorostyrenes; cyano-styrenes, such as ortho-, meta-, and para cyano styrenes, dicyano styrenes; nuclear-substituted alkyl-styrenes, such as monoand di-methyl-styrenes, monoand di-ethylstyrenes, monoand di-isopropyl-styrenes; arylsubstituted styrenes, i. e., para-phenyl-styrene, etc; cycloaliphatic-substituted styrenes, such as para-cyclohexyl-styrene; fluoro-styrenes, such as ortho-, meta-, and para-fluoro-styrene, difluorostyrenes, etc.; trifiuoro-methyl-styrenes, such as ortho-, meta-, and para-trifluoromethyl-styrenes, di-(trifiuoromethyl)-styrenes, and various other styrenes or mixtures of any number of these with each other or with styrene.

The procedure of this example may also be used with various other amide esters set forth above.

Example VI The procedure of Example I is repeated for the polymerization of the following monomer compositions:

Methyl ester of Acrylo- Vmylidcne v qumolyl) Copolymer P013 met gg g' 335 maleic amide Soluble in acid, Parts A 85 5 l0 DlVgF, DMA

e c. B 65 25 10 DlViF, DMA,

e c. C 45 45 1O Dl\1gF,Dl\iA,

e c. D .25 65 10 DMfF, DMA,

e c. E 5 85 1O DMF,DMA,

etc. 5

Example VII The procedure of Example I is repeated for the polymerization of the following monomer compositions:

The dyeing tests of the copolymer products show dye susceptibility similar to the copolymers of Example I.

The procedure of this example may also be used with the various other amide esters set forth above.

Example VIII Instead of copolymerizing the N-pyridyl malelc acid amides with the acrylonitrile, copolymers of the amide, such as polymers D and E of Example II, may be used as modifiers for the unmodified homopolymers and copolymers of acrylonitrile. For example, polymer E of Example II, which consists of parts of acrylonitrile and 20 parts of methyl ester of N-(Z-pyridyl) maleic amide acid, has excellent compatibility with homopolymers of acrylonitrile. In many cases, it is desirable to use the copolymers of the N- pyridyl maleic acid amides, which have even a higher ratio of the maleic acid amide, as for example, as high as equal molar ratios of the maleic acid amide copolymerized with acrylonitrile or methacrylonitrile. Suitably from about 10 to 15 to about 70 per cent of amide may be used. The overall amounts of amide required to improve the dyeability generally corresponds to the amounts indicated above for copolymers in which the main body of the acrylonitrile polymers contain the amide oopolymerized directly therein, that is, at least about 0.1 per cent and advantageously up to 5 per cent or even 15 per cent amide may be desirable in the ultimate polymer mixture. The copolymers of maleic acid amides with other monomers are satisfactory such as, for example, copolymers of styrene, methyl acrylate, ethyl methacrylate, alphamethyl-styrene, etc., and these copolymers may be prepared substantially in accordance with the procedure of Example I. A solution of these copolymers is prepared in dimethyl formamide and added to a dimethyl formamide solution of polyacrylonitrile, so that a composition containing parts combined acrylonitrile and other monomer units and about 10 parts of the amide units is obtained. The solution is heated to C. after which the solution is filtered. Films and fibers prepared from this mixture are dyed in accordance with the process of Example III and satisfactory dyed, shaped articles are obtained. The unmodified polyacrylom'trile without the addition of these maleic acid amides shows little or no dye retention.

When it is desired to modify an acrylonitrile copolymer such as the copolymer of acrylonitrile and styrene or the copolymers of acrylonitrile and other copolymerizable ethylenic compounds, it is usually desirable to use as modifiers copolymers containing at least one structural unit present in the acrylonitrile copolymer. Thus as there are present in the achylonitrile copolymer, structural. :units derived .zf-rom ithe zacrylor'iit-rile. and styrene, it :lsdesirable to have presentinrthe modifying .copolymer structural units derived fromastyrene and/or.acrylonitrile,= advantageously both, in addition to .thosederived from the amide. By thus including in the-.modifying lcopolymers structural units ofthe :same type as :the structural units of the :ccpolymer to :be' modified, greater compatibility between the acrylonitrile copolymer to .be modified and the modifying copolymer is obtained and the 'zllWO are :lrnore readily soluble in the mutual solvent and :"will more readily mix into homogeneous polymer mixtures.

The di-N-pyridyl -amides of the structure'z' in which R and R and P are as above indicated may be used instead of the monoamide in the practice of the invention.

The polymerization products of the present invention have in the polymer molecule .a plurality of repeating units of the formula in which R, Y and Z are indicated-above and will contain additional repeating -.--units of the formula CH2-'CH when the amide is copolymerized with .acry-lonitrile.

In addition, the polymerization products may contain any number of -repeating units .of the type obtained by thecopolymerization of. the- N-(pyridyh amide or a mixture of acrylonitrile and the amide with one or more copolymerizable ethylenic compounds, suchas, for example, vinylidene chloride, vinyl chloride, styrene, alphamethyl-styrene and methacrylonitrile. When the polymerizable mass contains, in addition to the pyridyl amide derivative, a polymerizalole monomer having a CH2=C group in an amount such that the latter monomer is present to an extent of at least 50 mole per cent of the overall monomer content, then monomers such as fumaronitrile, beta-cyano-acrylamide and methyl betacyano-acrylate may also be present in the polymerization mixture.

As previously indicated, the solvent resistance of such copolymers-as contain one or more monouser units in addition to those formed by the acrylonitrile and the N-(pyridyl) amide is affected by the type and proportion of copolymerizing monomer or monomers used to replace part of the acrylonitrile. For example, copolymers containing small amounts of the 'N- (pyridyl) amide units may contain various proportions of such monomer units as obtained from vinylidene chloride, methacrylonitrile, fumaronitrile, and beta-cyano-acrylamide without considerable reduction in solvent resistance. acrylonitrile units in the copolymers by vinyl chloride, styrene and alpha-methyl-styrene units results in copolymers of lowered solvent resistance, the amount of such lowering in resistance in each case depending on the amount substi-- tuted. In addition to the solvent resistance, certain other physical properties of the copolymers are affected by the presence of these additional units in the .copolymers. The amount and char Replacement of 4 1.0 acter .of theachanges :in iphysicalxproperties :of these copolymers depend again on "the type and proportion of .copolymerizin'g. monomer :or monomers used. For example, the tensilestrength 'of an :acrylonitrile 'N-:(pyridyl') imaleic :acid amide type copolymer will decrease much more when .a monomer-having relativelyweak secondary bond ing forces, such as styrene or ethylene is used to replace part .ofthe acrylonitrile than when \one 01"211'10118' :moncrners" haying relatively ,strong bonding forces, such "asumethacr-ylonitrile, fue maronitrile, betacyano acrylamide, methyl betaecyano-acrylate and :vinylidene chloride, is used to replace :part 0fthe acrylonitrile. Moreover, the ability 10f \these -:copo1ymers to form molecularly oriented rshaped articles depends on the type and amount of the-copolymerizing .mon-

omer or monomersrused'to replace acrylonitrile.. Gther copolymerizable iethylenic compounds,

which may also be present in the polymerizable masses for copolymerization with the amides of.

thisinvention include one or more -of the following: acrylates, 4e. g.,met-hyl acrylate; methacrylates, e. g., methyl methacr-ylates; acrylamides; me'thacrylamides; vinyl esters, such as vinyl acetate; i-taconic diesters, such as dimeth-yl. and :diethyl 'itaconates; itaconamide; vinyl halides, such as vinylwfluori'de, vinylidene fluoride,

tetrafluoroethylene, tri-fluorochloroethylene; vinylv ary-ls, such as vinyl ,naphthalenes and the n-uclear-. substituted .styreneslisted in Example V, etc.

The polymerization products of this inventionv may be prepared by 'yarious vpolymerization systems, such as emulsion, suspension, mass, and solution polymerizations. In addition @to the monomers, the polymerizable mass may also con-v tain other materials such as catalysts, e.-'.g.,i peroxides, such as benzoyl peroxide, naphthyl peroxides, phthalyl peroxide, tertiary-butylhydroperoxide, hydrogen hydroperoxide, tertiary-butyl-perbenzoate, etc., azo catalysts, persulfates, such as ammonium persulfate, etc., solvents, suspension or emulsion media, emulsifying agents, :suspens-ion agents,

plasticizers, lubricants, etc.

For use inthe preparation :of shaped articles, the polymerization products of this invention have molecular :weights preferably of at leastabout 10,000. However, polymerization products of molecular "Weights .less than 10,000 may .be. used for otherpurposes, such rasimpregnants,

The molecularsolvent resistant ooatings, etc. Weight of the polymerization products is dependent on the concentrations of the monomers, the amount and-type ofcatalyst, the temperature or reaction, etc.- i

As is quite'generally'known in the field-of high polymers, molecular orientation is usually indi-- cated and identified by birefringence ofpolarized light, as under Nicol prisms,-by increased density as compared to the density of the same polymer unoriented, and by characteristic X-ray difiraction patterns. When a material is crystalline or oriented, its X-ray diagramshows bright areas or spots for-points of crystallization and dark areas for the non-crystalline regions. The intensity .or number of these bright spots increases with the degree of orientation-or crystallization. .Amorphous or non-crystalline materials give .X-ray. diagrams having very few high lights .or bright:

spots whereas crystalline orcoriented materials give definite X-ray diffraction patterns. In these patterns there are definite'relationships of the bright spots with regard to position and spacing which are generally .characteristic of the compercxide, cyclohexyl position of the material being X-rayed. In fibers or 'films the orientation usually follows the direction of drawing or stretching so that the orientation is parallel to the fiber axis or a major surface.

Useful fibers may be made from the solutions of the copolymers of this invention by dry spinning, as in the preparation of cellulose acetate fibers, or by wet spinning, as in the preparation of viscose rayon. In wet spinning, the solution of copolymer may be spun into a substance which is a nonsolvent for the copolymer, but which is advantageously compatible with the solvent in which the copolymer is dissolved. For example, water, acetone, methyl aclohol, carbon disulfide, glycerine, chloroform, carbon tetrachloride, benzene, etc., may be used as a precipitating bath for N,N-dimethyl acetamide, N,N,N',N'-tetramethyl urea, butyrolactone, ethylene carbonate, and other solvent compositions of these copolymers. The extruded fibers, from which substantially all of the solvent has been removed in the spinning step, about 1-10 per cent remaining in the shaped article, may then be cold-drawn about 100-900 per cent, preferably about 300-600 per cent; and the drawn fiber heat-treated, usually at substantially constant length, at about 100-160 C. to effect further crystallization and removal of the remaining solvent. The term heat-treated, as used herein, refers to the application of heat to an object, usually at a controlled temperature and usually by means of the medium surrounding the object.

Many of the acrylonitrile copolymers of this invention may be molecularly oriented, especially if there is no more than per cent N- (pyridyl) amide in the polymer molecule. This is true when the major portion of the copolymer is acrylonitrile, for example, 85 per cent or more acrylonitrile, or when the other copolymerizing monomers used in making such copolymers have substituent groups having secondary valence bonding forces equal to or greater than exhibited by the cyano group in acrylonitrile. For example, if such monomers as methacrylonitrile, fumaronitrile, vinylidene chloride, beta-cyanoacrylamide and methyl beta-cyano-acrylate are used with acrylonitrile and the N-(pyridyl) amide, the proportion of acrylonitrile in the copolymers may be much less than 85 per cent without destroying the capacity for molecular orientation. Molecularly oriented, cold-drawn, shaped articles of particular usefulness are prepared from copolymer compositions containing in the polymer molecules 60-99.9 per cent acrylonitrile, 01-15 per cent, advantageously 01-5 per cent, N-(pyridyl) amide, with or without one or more monomers of the class consisting of vinylidene chloride, vinyl chloride, styrene, alphamethyl-styrene, methacrylonitrile, fumaronitrile, beta-cyano-acrylamide and methyl beta-cyano acrylate, the effects of the presence of the monomers of this class being noticeable when the monomer is present in the polymer molecule in amounts of 1 per cent or more.

The polymerization products of this invention show great afiinity for the acetate, basic, acidic and vat dyes. The cellulose acetate dyes which are effective with these polymerization products are mainly amino-anthraquinone derivatives. The basic dyestufis toward which these polymerization products show great afiinity are preferably those which contain amido, alkylamido, or ammonium groups, such as -NH2, N(CHs)z, -N(C2H5)2, NHC6H5, -(CH3)3OH, etc. and which may also be used in the form of their tate dyes which are effective with these polymerization products are mainly amino-anthraquinone derivatives, basic azo compounds and other basic substances, such as the Duranol, Dispersol, Sericol, etc. dyestufis. A number of other acidic dyes that can be used are anthranilic acid 1-(4'-sulfophenyl) 3 methyl 5 pyrazolone; 1,5 diamino 4,8 dihydroxyanthraquinone 3- sulfonic acid; the 1-aminonaphthalene-4-sul ionic acid alpha-naphthol-4-sulfonic acid; the sodium salt of sulfanilic acid aniline- 2-benzoyl-amino 5 naphthol 7 sulfonic acid; the sodium salt of 4,4-diaminostilbene-2,2'-di-sulionic acid 3 (phenohz ethylated; 1,5-diamino- 4,8 dihydroxyanthraquinone 3 sulfonic acid; dye prepared by diazotizing l-aminonaphthalenel-sulfonic acid and coupled with alphanaphtholl-sulfonic acid; the sodium salt of (m aminobenzoic acid o anisidene) phosgenated; the sodium salt of (2-naphthol-6,8- disulfonic acid benzidineephenol) ethylated; dimethoxy-dibenzathrone; and 1,5-di-p-anisoylamino-4,8-diehydroxyanthraquinone.

From the molecularly orientable copolymers of this invention fibers may be prepared having improved dyeing properties, low shrinkage in boiling water, sometimes as low as 3 to 5 per cent or less of the cold-drawn or stretched article, good heat resistance, and tensile strength in the order of 4 to 6 grams per denier. Moreover, these properties make the fibers desirable in the manufacture of hosiery and for such allpurpose fabrics as used for blouses, shirts, suits, etc.

I claim:

1. A polymeric composition having in the polymer molecule aplurality of repeating units having the formula selected from the class consisting of in which Y is selected from the class consisting of piperidyl, piperazino, and morpholino; R is selected from the class consisting of hydrogen and alkyl, aryl, aralkyl, alkaryl, and cycloaliphatic groups; R is selected from the class consisting of hydrogen and the methyl radical; R" is an alkyl group containing not more than three carbon atoms and P is the pyridyl group which can be substituted with hydrocarbon substituents containing not more than 5 carbon atoms.

2. A polymeric composition having in the polyconsisting of vinyl chloride,

mer molecule a plurality of repeating units having the formula N 3. The polymerization product of claim 2 which contains in the polymer molecule a plurality of 7 atoms, said copolymer having a molecular Weight of at least about 10,000 and containing in the polymer molecule no more than about 15 per cent by weight of said amide.

6. A cold-drawn fiber having molecular orientation, said fiber comprising a copolymer of about 60-989 per cent by weight acrylonitrile, about 0.1 to per cent by weight N-pyridyl amide of an alkene-l,2-dioic acid containing not more than five carbon atoms, and about 1 to 39.9 per cent by weight of a compound selected from the class vinylidene chloride, styrene, alpha-methyl-styrene, methacrylonitrile, fumaronitrile, beta-cyano-acrylamide, and methyl beta-cyano-acrylate.

7. A cold-drawn fiber having molecular orientation, said fiber comprising a copolymer of about 60-989 per cent by weight acrylonitrile, about 0.1 to 5 per cent by weight N-pyridyl amide of an alkene-1,2-dioic acid containing not more than five carbon atoms, and about 1 to 39.9 per cent by weight vinylidene chloride.

8. A cold-drawn fiber having molecular orientation, said fiber comprising a copolymer of about 60-98.!) per cent by weight acrylonitrile, about 0.1 to 5 per cent by weight N-pyridyl amide of an alkene-L2-dioic acid containing not more than five carbon atoms, and about 1 to 39.9 per cent by weight vinyl chloride.

9. A cold-drawn fiber having molecular orientation, said fiber comprising a copolymer of about 6098.9 per cent by weight acrylonitrile, about 0.1 to 5 per cent by weight N-pyridyl amide of an alkene-1,2-dioic acid containing not more than five carbon atoms, and about 1 to 39.9 per cent by Weight styrene.

10. A cold-drawn fiber having molecular orien-' tation, said fiber comprising a copolymer of about -989 per cent by Weight acrylonitrile, about 0.1 to 5 per cent by weight an amide having the following formula H-CO- H-CO N and about 1 to 39.9 per cent by weight of a compound selected from the class consisting of vinyl chloride, vinylidene chlor'de, styrene, alpham'ethyLstyrene, methacrylonitrile, fumaronitrile, beta-cyano-acrylamide, and. methyl beta-cyanoacrylate.

1].. A polymeric composition in the polymer molecule a plurality of repeating units having the formula 12. The polymerization product of claim 11 which contains in the polymer molecule a plurality of repeating units of the formula 13. A cold-drawn fiber having molecular orien-- tation, said fiber comprising a copolymer of about 60-989 per cent by weight acrylonitrile, about 0.1 to 5 per cent by weight an amide having the following formula OCHa-CO CHsO- ll NH References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,508,860 Grimmel May 23, 1950 2,531,410 DAlelio Nov. 28, 1950 

1. A POLYMERIC COMPOSITION HAVING IN THE POLYMER MOLECULE A PLURALITY OF REPEATING UNITS HAVING THE FORMULA SELECTED FROM THE CLASS CONSISTING OF 